Bulk and solution polymerization of isobutene using tris(pentafluorophenyl) gallium and tris(pentafluorophenyl)aluminum

Nathan Hand, Robert Timothy Mathers, Krishnan Damodaran, Stewart P. Lewis

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

From the standpoint of green chemistry, tris(pentafluorophenyl)gallium (7) and tris(pentafluorophenyl)aluminum (8) outperform all previously explored perfluoroarylated Lewis acids (PFLAs) for the polymerization of isobutene. In comparison to other PFLA based systems, 7 and 8 do not require ultrahigh purity monomer, toxic chlorinated solvents, or expensive and highly sensitive initiators (e.g., metallocenes). Moreover, compared to other PFLA based initiator systems they provide much larger yields of high to medium molecular weight polyisobutene even at polymerization temperatures up to ambient. Stopping experiments indicate that strong Brønsted acids formed in situ by reaction with adventitious moisture (9 and 10, respectively) induce cationic polymerization protonically. Unlike other PFLA compounds which require expensive and/or energetically unstable precursors, 7 and 8 are readily synthesized from their corresponding group 13 halides in conjunction with bis(pentafluorophenyl) zinc (6), thereby lending themselves to commercial implementation.

Original languageEnglish (US)
Pages (from-to)2718-2725
Number of pages8
JournalIndustrial and Engineering Chemistry Research
Volume53
Issue number7
DOIs
StatePublished - Feb 19 2014

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Lewis Acids
Gallium
Aluminum
Polymerization
Acids
Cationic polymerization
Poisons
Organometallics
Zinc
Moisture
Monomers
Molecular weight
isobutylene
Experiments
Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

Cite this

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abstract = "From the standpoint of green chemistry, tris(pentafluorophenyl)gallium (7) and tris(pentafluorophenyl)aluminum (8) outperform all previously explored perfluoroarylated Lewis acids (PFLAs) for the polymerization of isobutene. In comparison to other PFLA based systems, 7 and 8 do not require ultrahigh purity monomer, toxic chlorinated solvents, or expensive and highly sensitive initiators (e.g., metallocenes). Moreover, compared to other PFLA based initiator systems they provide much larger yields of high to medium molecular weight polyisobutene even at polymerization temperatures up to ambient. Stopping experiments indicate that strong Br{\o}nsted acids formed in situ by reaction with adventitious moisture (9 and 10, respectively) induce cationic polymerization protonically. Unlike other PFLA compounds which require expensive and/or energetically unstable precursors, 7 and 8 are readily synthesized from their corresponding group 13 halides in conjunction with bis(pentafluorophenyl) zinc (6), thereby lending themselves to commercial implementation.",
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Bulk and solution polymerization of isobutene using tris(pentafluorophenyl) gallium and tris(pentafluorophenyl)aluminum. / Hand, Nathan; Mathers, Robert Timothy; Damodaran, Krishnan; Lewis, Stewart P.

In: Industrial and Engineering Chemistry Research, Vol. 53, No. 7, 19.02.2014, p. 2718-2725.

Research output: Contribution to journalArticle

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AU - Lewis, Stewart P.

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